Compositions comprising e-1,1,1,4,4,4-hexafluoro-2-butene and uses thereof

ABSTRACT

The present disclosure relates to compositions comprising E-1,1,1,4,4,4-hexafluoro-2-butene and additional compounds that may be useful as refrigerants, heat transfer compositions, aerosol propellants, foaming agents, blowing agents, solvents, cleaning agents, carrier fluids, displacement drying agents, buffing abrasion agents, polymerization media, expansion agents for polyolefins and polyurethane, gaseous dielectrics, power cycle working fluids, extinguishing agents, and fire suppression agents in liquid or vapor form, and in methods for detecting leaks.

FIELD OF THE INVENTION

The present disclosure relates to the field of compositions which may beuseful as refrigerants, heat transfer compositions, thermodynamic cycle(e.g. heating or cooling cycle) working fluids, aerosol propellants,foaming agents (blowing agents), solvents, cleaning agents, carrierfluids, displacement drying agents, buffing abrasion agents,polymerization media, foaming agents for polyolefins and polyurethane,gaseous dielectrics, power cycle working fluids, extinguishing agents,and fire suppression agents in liquid or gaseous form.

BACKGROUND OF THE INVENTION

New environmental regulations have led to the need for new compositionsfor use in refrigeration, air-conditioning, heat pump and power cycleapparatus and many other areas of use. Low global warming potentialcompounds are of particular interest.

SUMMARY OF THE INVENTION

Applicants have found that in preparing such new low global warmingpotential compounds, such as 1,1,1,4,4,4-hexafluoro-2-butene, thatcertain additional compounds are present.

Therefore, in accordance with the present invention, there is provided acomposition comprising E-1,1,1,4,4,4-hexafluoro-2-butene and at leastone additional compound selected from the group consisting ofHFO-1243zf, HCC-40, HCFO-1223, CFC-113a, CFC-113, HFO-1429, HFC-449,HFC-365, HFO-1327, HFO-1132, HCFC-123a, chlorobutane, ethyl benzene,o-xylene, m-xylene, and p-xylene. The composition may contain less thanabout 1 weight percent of the at least one additional compound, based onthe total weight of the composition.

DETAILED DESCRIPTION Compositions

E-1,1,1,4,4,4-hexafluoro-2-butene (E-HFO-1336mzz) has been suggested foruse as a refrigerant, heat transfer fluid, foam expansion agent, powercycle working fluid, among other uses. It has also, advantageously, beenfound that E-HFO-1336mzz has a low global warming potential (GWP),GWP=32. Thus, E-HFO-1336mzz is a good candidate for replacing some ofthe higher GWP saturated CFC (chlorofluorocarbon), HCFC(hydrochlorofluorocarbon), or HFC (hydrofluorocarbon) refrigerants.

E-1,1,1,4,4,4-hexafluoro-2-butene (also known as E-HFO-1336mzz orcis-HFO-1336mzz and having the structure cis-CF₃CH═CHCF₃), may be madeby methods known in the art, such as by hydrodechlorination of2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene, as described in U.S.Patent Application Publication No. US 2009/0012335A1, incorporatedherein by reference.

In one embodiment, the present disclosure provides a compositioncomprising E-HFO-1336mzz and at least one additional compound selectedfrom the group consisting of HFO-1243zf (3,3,3-trifluoropropene), HCC-40(chloromethane, CH₃Cl), HCFO-1223 (C₃HF₃Cl₂), CFC-113a (CF₃CCl₃),CFC-113 (CF₂ClCCl₂F), HFO-1429 (C₅HF₉), HFC-449 (C₅H₃F₉), HFC-365(C₄H₅F₅), HFO-1327 (C₄HF₇), HFO-1132 (CHFCHF), HCFC-123a (CHClFCClF₂),chlorobutane, ethyl benzene, o-xylene, m-xylene, and p-xylene, HCFO-1334(C₄H₂F₄Cl₂), HCFO-1333 (C₄H₂F₃Cl₃), CFC-11 (trichlorofluoromethane,CFCl₃), and combinations thereof. HFO-1243zf, HCC-40, CFC-113, CFC-113a,CFC-11, chlorobutane, ethylbenzene, m-xylene, and p-xylene are availablecommercially or can be made by processes known in the art. The remainingfluorocarbon compounds can be purchased from a specialty fluorochemicalsupplier, such as SynQuest Laboratories, Inc. (Alachua, Fla., USA) ormade by processes known in the art.

The compositions of the present invention may comprise E-HFO-1336mzz andone additional compound, or two additional compounds, or three or moreadditional compounds.

In one embodiment, the total amount of additional compound(s) in thecomposition comprising E-HFO-1336mzz ranges from greater than zeroweight percent to less than 1.0 weight percent, based on the totalweight of the composition. In another embodiment, the total amount ofadditional compound(s) ranges from greater than zero weight percent toless than 0.5 weight percent, based on the total weight of thecomposition. In another embodiment, the total amount of additionalcompound(s) ranges from 0.01 ppm(weight) to about 1 weight percent. Inanother embodiment, the total amount of additional compound(s) rangesfrom 0.1 ppm(weight) to about 1 weight percent. In another embodiment,the total amount of additional compound(s) ranges from 0.001 weightpercent to about 1 weight percent. In another embodiment, the totalamount of additional compound(s) ranges from 0.001 weight percent toabout 0.5 weight percent.

In one embodiment, the compositions comprising E-HFO-1336mzz and othercompounds may further comprise at least one tracer compound. Theinclusion of tracer compounds is useful to determine the occurrence ofdilution, adulteration or contamination; or to verify the source of thecomposition. The tracer compound(s) may be selected from the groupconsisting of HFC-356 (e.g., HFC-356mff), HCFC-123(2,2-dichloro-1,1,1-trifluoroethane, CF₃CHCl₂), HCFC-133a(2-chloro-1,1,1-trifluoroethane, CF₃CH₂Cl), HFC-143a(1,1,1-trifluoroethane, CF₃CH₃), HCFO-1122 (1-chloro-2,2-difluoroethene,CF₂═CHCl), HCFO-1122a (1-chloro-1,2-difluoroethene, CFH═CFCl), HCFO-1335(C₄H₂F₅Cl), HFO-1345 (C₄H₃F₅), HCFO-1326 (C₄HF₆Cl), CFO-1316 (C₄F₆Cl₂),HCFO-1334 (C₄H₂F₄Cl₂), HCFO-1333 (C₄H₂F₃Cl₃), and combinations thereof.In this embodiment, the tracer compound(s) may be present at aconcentration from about 0.01 part per million (ppm) to about 1000 ppmin the composition. In another embodiment, the tracer compound(s) may bepresent at a concentration from about 0.01 ppm to about 500 ppm. Inanother embodiment, the tracer compound(s) may be present at aconcentration from about 0.1 ppm to about 500 ppm. In anotherembodiment, the tracer compound(s) may be present at a concentrationfrom about 1 ppm to about 500 ppm. In another embodiment, the tracercompound(s) may be present at a concentration from about 10 ppm to about500 ppm. Alternatively, the tracer compound(s) may be present at aconcentration from about 10 ppm to about 300 ppm.

In another embodiment, the compositions of the present inventioncomprise a composition selected from the group consisting of:

-   -   E-HFO-1336mzz, HFO-1429, and HCFO-1335;    -   E-HFO-1336mzz, HFO-1429, and HFO-1345;    -   E-HFO-1336mzz, HFO-1429, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429, and CFC-11;    -   E-HFO-1336mzz, HFO-1429, HCFO-1335, and HFO-1345;    -   E-HFO-1336mzz, HFO-1429, HCFO-1335, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429, HCFO-1335, and CFC-11;    -   E-HFO-1336mzz, HFO-1429, HFO-1345, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429, HFO-1345, and CFC-11;    -   E-HFO-1336mzz, HFO-1429, HCFO-1335, HFO-1345, and HCFC-123;    -   E-HFO-1336mzz, HCFO-1335, and HFO-1345;    -   E-HFO-1336mzz, HCFO-1335, and HCFC-123;    -   E-HFO-1336mzz, HCFO-1335, and CFC-11;    -   E-HFO-1336mzz, HCFO-1335, and HCFO-1334;    -   E-HFO-1336mzz, HCFO-1335, HFO-1345, and HCFC-123;    -   E-HFO-1336mzz, HFO-1345, and HCFC-123;    -   E-HFO-1336mzz, HFO-1345, and CFC-11;    -   E-HFO-1336mzz, HFC-365, and HCFO-1326;    -   E-HFO-1336mzz, HFC-365, and CFC-11;    -   E-HFO-1336mzz, HFO-1243zf, and HCFO-1122;    -   E-HFO-1336mzz, HFO-1243zf, and HCC-40;    -   E-HFO-1336mzz, HCFO-1122, and HCC-40;    -   E-HFO-1336mzz, HFO-1243zf, HCFO-1122, and HCC-40;    -   E-HFO-1336mzz, CFC-113a, and HFC-365; and    -   E-HFO-1336mzz, CFC-113a, and CFC-11.

In one embodiment of the compositions disclosed herein HFO-356 isHFO-356mff (1,1,1,4,4,4-hexafluorobutane, or CF₃CH₂CH₂CF₃).

In one embodiment of the compositions disclosed herein CFO-1316 isE-CFO-1316mxx (E-CF₃CCl═CClCF₃), Z-CFO-1316mxx (Z-CF₃CCl═CClCF₃), orcombinations thereof.

In one embodiment of the compositions disclosed herein HFO-1327 isE-HFO-1327mzx (E-CF₃CH═CFCF₃), Z-HFO-1327mzx (Z-CF₃CH═CFCF₃), orcombinations thereof.

In one embodiment of the compositions disclosed herein HCFO-1335 isHCFO-1335mzz (CF₃CH═CHCF₂Cl), HCFO-1335mzx, (CF₃CH═CClCF₂H), orcombinations thereof. In another embodiment, HCFO-1335 isE-HCFO-1335mzz, Z-HFO-1335mzz, or combinations thereof. In anotherembodiment, HCFO-1335 is E-HCFO-1335mzx, Z-HCFO-1335mzx or combinationsthereof.

In one embodiment of the compositions disclosed herein HFO-1345 isHFO-1345mzz (CF₃CH═CHCF₂H), HFO-1345 cm (CF₃(CH₃)C═CF₂), or combinationsthereof. In another embodiment, HFO-1345 is E-HFO-1345mzz orZ-HFO-1345mzz. In another embodiment HFO-1345 is HFO-1345 cm.

In one embodiment of the compositions disclosed herein HCFO-1326 isE-HCFO-1326mxz (E-CF₃CCl═CHCF₃), Z-HCFO-1326mxz (Z-CF₃CCl═CHCF₃), orcombinations thereof.

In one embodiment of the compositions disclosed herein HFO-1429 isHFO-1429mzy (CF₃CH═CFCF₂CF₃), HFO-1429myz (CF₃CF═CHCF₂CF₃), HFO-1429cz(CF₂═CHCF₂CF₂CF₃), HFO-1429cye (CF₂═CFCHFCF₂CF₃), or combinationsthereof. In another embodiment, HFO-1429 is E-HFO-1429mzy orZ-HFO-1429mzy. In another embodiment, HFO-1429 is E-HFO-1429myz orZ-HFO-1429myz. In another embodiment HFO-1429 is HFO-1429cz. In anotherembodiment, HFO1429 is HFO-1429cye.

In one embodiment of the compositions disclosed herein HFC-449 isHFC-449mfe (CF₃CF₂CHFCH₂CF₃), HFC-449mmzf ((CF₃)₂CHCH₂CF₃), orcombinations thereof. In another embodiment, HFC-449 is HFC-449mfe. Inanother embodiment, HFC-449 is HFC-449mmzf.

In one embodiment of the compositions disclosed herein HCFO-1223 isHCFO-1223za (CF₃CH═CCl₂).

In one embodiment of the compositions disclosed herein HFC-365 isHFC-365mfc.

In one embodiment of the compositions disclosed herein chlorobutane is1-chlorobutane, 2-chlorobutane, or combinations thereof.

In one embodiment of the compositions disclosed herein HCFO-1334 isE-HCFO-1334mzz (E-CF₃CH═CHCFCl₂), Z-HCFO-1334mzz (Z-CF₃CH═CHCFC₂), orcombinations thereof.

In one embodiment of the compositions disclosed herein HCFO-1333 isE-HCFO-1333mzz (E-CF₃CH═CHCCl₃), Z-HCFO-1333mzz (Z-CF₃CH═CHCCl₃), orcombinations thereof.

Thus, in another embodiment the compositions of the present inventioncomprise a composition selected from the group consisting of:

-   -   E-HFO-1336mzz, HFO-1429myz, and HCFO-1335mzz;    -   E-HFO-1336mzz, HFO-1429myz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429myz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429myz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429myz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429myz, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429myz, HFO-1345mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429myz, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429myz, HFO-1345 cm, and CFC-11;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, HFO-1345mzz, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429myz, HCFO-1335mzz, HFO-1345 cm, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, and HCFO-1335mzz;    -   E-HFO-1336mzz, HFO-1429mzy, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429mzy, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429mzy, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, and CFC-11;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429mzy, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, HFO-1345mzz, and HCFC-11;    -   E-HFO-1336mzz, HFO-1429mzy, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, HFO-1345 cm, and CFC-11;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, HFO-1345mzz, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429mzy, HCFO-1335mzz, HFO-1345 cm, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, and HCFO-1335mzz;    -   E-HFO-1336mzz, HFO-1429cz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429cz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429cz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cz, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, HFO-1345mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cz, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, HFO-1345 cm, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, HFO-1345mzz, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429cz, HCFO-1335mzz, HFO-1345 cm, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, and HCFO-1335mzz;    -   E-HFO-1336mzz, HFO-1429cye, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429cye, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429cye, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, and HFO-1345mzz;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, and HFO-1345 cm;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cye, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, HFO-1345mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cye, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, HFO-1345 cm, and CFC-11;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, HFO-1345mzz, and        HCFC-123;    -   E-HFO-1336mzz, HFO-1429cye, HCFO-1335mzz, HFO-1345 cm, and        HCFC-123;    -   E-HFO-1336mzz, HCFO-1335mzz, and HFO-1345mzz;    -   E-HFO-1336mzz, HCFO-1335mzz, and HFO-1345 cm;    -   E-HFO-1336mzz, HCFO-1335mzz, and HCFC-123;    -   E-HFO-1336mzz, HCFO-1335mzz, and CFC-11;    -   E-HFO-1336mzz, HCFO-1335mzz, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HCFO-1335mzz, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1345mzz, and HCFC-123;    -   E-HFO-1336mzz, HFO-1345mzz, and CFC-11;    -   E-HFO-1336mzz, HFO-1345 cm, and HCFC-123;    -   E-HFO-1336mzz, HFO-1345 cm, and CFC-11;    -   E-HFO-1336mzz, HFC-365mfc, and HCFO-1326mxz;    -   E-HFO-1336mzz, HFC-365mfc, and CFC-11;    -   E-HFO-1336mzz, HFO-1243zf, and HCFO-1122;    -   E-HFO-1336mzz, HFO-1243zf, and HCFO-1122a;    -   E-HFO-1336mzz, HFO-1243zf, and HCC-40;    -   E-HFO-1336mzz, HCFO-1122, and HCC-40;    -   E-HFO-1336mzz, HCFO-1122a, and HCC-40;    -   E-HFO-1336mzz, HFO-1243zf, HCFO-1122, and HCC-40;    -   E-HFO-1336mzz, HFO-1243zf, HCFO-1122a, and HCC-40;    -   E-HFO-1336mzz, CFC-113a, and HFC-365mfc; and    -   E-HFO-1336mzz, CFC-113a, and CFC-11.

The presence of additional compounds and/or tracer compounds in a sampleof E-HFO-1336mzz may be used to identify the process by which thecompound was manufactured. Thus, the additional compounds and/or tracercompounds may be used to detect infringement of chemical manufacturingpatents claiming the process by which the sample may have beenmanufactured. Additionally, the additional compounds and/or tracercompounds may be used to identify whether product is produced by thepatentee or some other entity, who may infringe product related patents.

Additional compounds and/or tracer compounds may provide improvedsolubility for active ingredients in an aerosol or polymer constituentsof a foam. Additionally, for refrigerant applications, such as use inair conditioning, heat pumps, refrigeration, and power cycles (e.g.,organic Rankine cycles), the additional compounds may provide improvedsolubility with refrigeration lubricants, such as mineral oils,alkylbenzenes, synthetic paraffins, synthetic naphthenes,poly(alpha)olefins, polyol esters (POE), polyalkylene glycols (PAG),polyvinyl ethers (PVE), or perfluoropolyethers (PFPE) or mixturesthereof.

In certain embodiments, additional compounds and/or tracer compoundscontaining at least one chlorine atom may provide improved solubilityfor active ingredients in an aerosol or polymer constituents of a foam.

Unsaturated fluorocarbons, such as E-HFO-1336mzz, exhibit differentsolubility than other typically used fluorocarbon propellants. Theirreduced solubility can make it difficult to produce single phase aqueoushomogenous aerosol formulations. The presence of low level chlorinatedimpurities can improve mixing and ease formulations and use of aerosolproducts.

Unsaturated fluorocarbons, such as E-HFO-1336mzz, also exhibit differentsolubility than other typically used blowing agents. Their reducedsolubility can act to help seed small cell growth during the foamingreaction but they can be difficult to mix. The presence of low levelchlorinated impurities can improve mixing and foam processingperformance without sacrificing the benefits from the lower HFOsolubility. Also, the chlorinated compounds typically have lower vaporthermal conductivities and so will impart improved insulatingperformance to a foam insulation product.

Additionally, for refrigerant applications, such as use in airconditioning, heat pumps, refrigeration, and power cycles (e.g., organicRankine cycles), the additional compounds containing at least onechlorine atom may provide improved solubility with refrigerationlubricants, such as mineral oils, alkylbenzenes, synthetic paraffins,synthetic naphthenes, poly(alpha)olefins, polyol esters (POE),polyalkylene glycols (PAG), polyvinyl ethers (PVE), orperfluoropolyethers (PFPE) or mixtures thereof.

Further, additional compounds may serve to improve leak detectionability. Leakage of refrigerants may lead to loss of refrigerant from asystem, thus increasing cost of operation due to the need to top offrefrigerant charge. And even minor loss of refrigerant from a system mayimpact proper operation. Finally, leakage of refrigerant may lead toexcessive environmental contamination. In particular, chlorinatedcompounds, even at low levels can increase the detectability ofrefrigerant at the point of a leak. Thus, the system may be repaired orredesigned to prevent refrigerant leakage.

The levels of chlorinated compounds must be kept low, however, becausehigher levels may create compatibility problems with materials ofconstruction. In aerosols, these compatibility problems may be with theaerosol container (e.g. cans), or with plastic valve parts. In foams,these compatibility problems may be with equipment seals and gaskets.Additionally, in aerosol products interaction of higher levels ofchlorinated compounds may cause formulation instability. In foamproducts, higher levels of chlorinated compounds may soften the foamresulting in dimensional instability and poor strength of the foam.

The compositions disclosed herein comprising E-HFO-1336mzz are useful aslow global warming potential (GWP) heat transfer compositions,refrigerants, power cycle working fluids, aerosol propellants, foamingagents, blowing agents, solvents, cleaning agents, carrier fluids,displacement drying agents, buffing abrasion agents, polymerizationmedia, expansion agents for poly-olefins and polyurethane, gaseousdielectrics, fire extinguishing agents, and fire suppression agents inliquid or gaseous form. The disclosed compositions can act as a workingfluid used to carry heat from a heat source to a heat sink. Such heattransfer compositions may also be useful as a refrigerant in a cyclewherein the fluid undergoes a phase change; that is, from a liquid to agas and back or vice versa.

Examples of heat transfer systems include but are not limited to airconditioners, freezers, refrigerators, heat pumps, water chillers,flooded evaporator chillers, direct expansion chillers, walk-in coolers,heat pumps, mobile refrigerators, mobile air conditioning units andcombinations thereof.

In one embodiment, the compositions comprising E-HFO-1336mzz are usefulin mobile heat transfer systems, including refrigeration, airconditioning, or heat pump systems or apparatus. In another embodiment,the compositions are useful in stationary heat transfer systems,including refrigeration, air conditioning, or heat pump systems orapparatus.

As used herein, mobile heat transfer systems refers to anyrefrigeration, air conditioner, or heating apparatus incorporated into atransportation unit for the road, rail, sea or air. In addition, mobilerefrigeration or air conditioner units, include those apparatus that areindependent of any moving carrier and are known as “intermodal” systems.Such intermodal systems include “containers’ (combined sea/landtransport) as well as “swap bodies” (combined road/rail transport).

As used herein, stationary heat transfer systems are systems that arefixed in place during operation. A stationary heat transfer system maybe associated within or attached to buildings of any variety or may bestand-alone devices located out of doors, such as a soft drink vendingmachine. These stationary applications may be stationary airconditioning and heat pumps (including but not limited to chillers, hightemperature heat pumps, including trans-critical heat pumps (withcondenser temperatures above 50° C., 70° C., 80° C., 100° C., 120° C.,140° C., 160° C., 180° C., or 200° C.), residential, commercial orindustrial air conditioning systems, and including window, ductless,ducted, packaged terminal, chillers, and those exterior but connected tothe building such as rooftop systems). In stationary refrigerationapplications, the disclosed compositions may be useful in hightemperature, medium temperature and/or low temperature refrigerationequipment including commercial, industrial or residential refrigeratorsand freezers, ice machines, self-contained coolers and freezers, floodedevaporator chillers, direct expansion chillers, walk-in and reach-incoolers and freezers, and combination systems. In some embodiments, thedisclosed compositions may be used in supermarket refrigerator systems.

Therefore in accordance with the present invention, the compositions asdisclosed herein containing E-HFO-1336mzz may be useful in methods forproducing cooling, producing heating, and transferring heat.

In one embodiment, a method is provided for producing cooling comprisingevaporating any of the present compositions comprising E-HFO-1336mzz inthe vicinity of a body to be cooled, and thereafter condensing saidcomposition.

In another embodiment, a method is provided for producing heatingcomprising condensing any of the present compositions comprisingE-HFO-1336mzz in the vicinity of a body to be heated, and thereafterevaporating said compositions.

In another embodiment, disclosed is a method of using the presentcompositions comprising E-HFO-1336mzz as a heat transfer fluidcomposition. The method comprises transporting said composition from aheat source to a heat sink.

The compositions disclosed herein may be useful as low global warmingpotential (GWP) replacements for currently used refrigerants, includingbut not limited to R-123 (or HFC-123,2,2-dichloro-1,1,1-trifluoroethane), R-11 (or CFC-11,trichlorofluoromethane), R-245fa (or HFC-245fa,1,1,1,3,3-pentafluoropropane), R-114 (or CFC-114,1,2-dichloro-1,1,2,2-tetrafluoroethane), R-236fa (or HFC-236a,1,1,1,3,3,3-hexafluoropropane), R-236ea (or HFC-236ea,1,1,1,2,3,3-hexafluoropropane), R-124 (or HCFC-124,2-chloro-1,1,1,2-tetrafluoroethane), among others.

In many applications, some embodiments of the present compositionscomprising E-HFO-1336mzz are useful as refrigerants and provide at leastcomparable cooling performance (meaning cooling capacity and energyefficiency) as the refrigerant for which a replacement is being sought.Additionally, the compositions of the present invention provide heatingperformance (meaning heating capacity and energy efficiency) comparableto a refrigerant being replaced.

In another embodiment is provided a method for recharging a heattransfer system that contains a refrigerant to be replaced and alubricant, said method comprising removing the refrigerant to bereplaced from the heat transfer system while retaining a substantialportion of the lubricant in said system and introducing one of thepresent compositions comprising E-HFO-1336mzz to the heat transfersystem. In some embodiments, the lubricant in the system is partiallyreplaced (e.g. replace a portion of the mineral oil lubricant used withfor instance, CFC-114 with a POE lubricant).

In another embodiment, the compositions of the present inventioncomprising Z-HFO-1336mzz may be used to top-off a refrigerant charge ina chiller. For instance, if a chiller using HCFC-114 has diminishedperformance due to leakage of refrigerant, the compositions as disclosedherein may be added to bring performance back up to specification.

In another embodiment, a heat exchange system containing any of thepresent compositions comprising E-HFO-1336mzz is provided, wherein saidsystem is selected from the group consisting of air conditioners,freezers, refrigerators, heat pumps, water chillers, flooded evaporatorchillers, direct expansion chillers, walk-in coolers, heat pumps, mobilerefrigerators, mobile air conditioning units, and systems havingcombinations thereof. Additionally, the compositions comprisingE-HFO-1336mzz may be useful in secondary loop systems wherein thesecompositions serve as the primary refrigerant thus providing cooling toa secondary heat transfer fluid that thereby cools a remote location.

Vapor-compression refrigeration, air-conditioning, or heat pump systemsinclude an evaporator, a compressor, a condenser, and an expansiondevice. A vapor-compression cycle re-uses refrigerant in multiple stepsproducing a cooling effect in one step and a heating effect in adifferent step. The cycle can be described simply as follows. Liquidrefrigerant enters an evaporator through an expansion device, and theliquid refrigerant boils in the evaporator, by withdrawing heat from theenvironment, at a low temperature to form a vapor and produce cooling.The low-pressure vapor enters a compressor where the vapor is compressedto raise its pressure and temperature. The higher-pressure (compressed)vapor refrigerant then enters the condenser in which the refrigerantcondenses and discharges its heat to the environment. The refrigerantreturns to the expansion device through which the liquid expands fromthe higher-pressure level in the condenser to the low-pressure level inthe evaporator, thus repeating the cycle.

In one embodiment, there is provided a heat transfer system containingany of the present compositions comprising E-HFO-1336mzz. In anotherembodiment is disclosed a refrigeration, air-conditioning or heat pumpapparatus containing any of the present compositions comprisingE-HFO-1336mzz. In another embodiment, is disclosed a stationaryrefrigeration or air-conditioning apparatus containing any of thepresent compositions comprising E-HFO-1336mzz. In yet another embodimentis disclosed a mobile refrigeration or air conditioning apparatuscontaining a composition as disclosed herein.

In another embodiment, the present invention relates to foam expansionagent compositions comprising E-HFO-1336mzz for use in preparing foams.In other embodiments the invention provides foamable compositions, andpreferably thermoset (like polyurethane, polyisocyanurate, or phenolic)foam compositions, and thermoplastic (like polystyrene, polyethylene, orpolypropylene) foam compositions and method of preparing foams. In suchfoam embodiments, one or more of the present compositions comprisingE-HFO-1336mzz are included as a foam expansion agent in foamablecompositions, which composition preferably includes one or moreadditional components capable of reacting and/or mixing and foamingunder the proper conditions to form a foam or cellular structure.

The present invention further relates to a method of forming a foamcomprising: (a) adding to a foamable composition a compositioncomprising E-HFO-1336mzz of the present invention; and (b) processingthe foamable composition under conditions effective to form a foam.

Another embodiment of the present invention relates to the use of thecompositions of the present invention comprising E-HFO-1336mzz aspropellants in sprayable compositions. Additionally, the presentinvention relates to a sprayable compositions comprising E-HFO-1336mzz.The active ingredient to be sprayed together with inert ingredients,solvents and other materials may also be present in a sprayablecomposition. In one embodiment, a sprayable composition is an aerosol.The present compositions can be used to formulate a variety ofindustrial aerosols or other sprayable compositions such as contactcleaners, dusters, lubricant sprays, mold release sprays, insecticides,and the like, and consumer aerosols such as personal care products (suchas, e.g., hair sprays, deodorants, and perfumes), household products(such as, e.g., waxes, polishes, pan sprays, room fresheners, andhousehold insecticides), and automotive products (such as, e.g.,cleaners and polishers), as well as medicinal materials such asanti-asthma and anti-halitosis medications. Examples of this includesmetered dose inhalers (MDIs) for the treatment of asthma and otherchronic obstructive pulmonary diseases and for delivery of medicamentsto accessible mucous membranes or intra-nasally

The present invention further relates to a process for producing aerosolproducts comprising the step of adding a composition of the presentinvention comprising E-HFO-1336mzz to a formulation, including active,ingredients in an aerosol container, wherein said composition functionsas a propellant. Additionally, the present invention further relates toa process for producing aerosol products comprising the step of adding acomposition of the present invention comprising E-HFO-1336mzz to abarrier type aerosol package (like a bag-in-a-can or piston can) whereinsaid composition is kept separated from other formulation ingredients inan aerosol container, and wherein said composition functions as apropellant. Additionally, the present invention further relates to aprocess for producing aerosol products comprising the step of addingonly a composition of the present invention comprising E-HFO-1336mzz toan aerosol package, wherein said composition functions as the activeingredient (e.g., a duster, or a cooling or freezing spray).

A process for converting heat from a heat source to mechanical energy isprovided. The process comprises heating a working fluid comprisingE-HFO-1336mzz and at least one additional compound, and optionally atleast one tracer compound and thereafter expanding the heated workingfluid. In the process the heating of the working fluid uses heatsupplied from the heat source; and expanding of the heated working fluidgenerates mechanical energy as the pressure of the working fluid islowered.

The process for converting heat may be a subcritical cycle, atrans-critical cycle or a supercritical cycle. In a transcritical cycle,the working fluid is compressed to a pressure above its criticalpressure prior to being heated, and then during expansion the workingfluid pressure is reduced to below its critical pressure. In a supercritical cycle, the working fluid remains above its critical pressurefor the complete cycle (e.g., compression, heating, expansion andcooling).

Heat sources include low pressure steam, industrial waste heat, solarenergy, geothermal hot water, low-pressure geothermal steam (primary orsecondary arrangements), or distributed power generation equipmentutilizing fuel cells or prime movers such as turbines, microturbines, orinternal combustion engines. One source of low-pressure steam could bethe process known as a binary geothermal Rankine cycle. Large quantitiesof low-pressure steam can be found in numerous locations, such as infossil fuel powered electrical generating power plants. Other sources ofheat include waste heat recovered from gases exhausted from mobileinternal combustion engines (e.g. truck or rail diesel engines orships), waste heat from exhaust gases from stationary internalcombustion engines (e.g. stationary diesel engine power generators),waste heat from fuel cells, heat available at combined heating, coolingand power or district heating and cooling plants, waste heat frombiomass fueled engines, heat from natural gas or methane gas burners ormethane-fired boilers or methane fuel cells (e.g. at distributed powergeneration facilities) operated with methane from various sourcesincluding biogas, landfill gas and coal-bed methane, heat fromcombustion of bark and lignin at paper/pulp mills, heat fromincinerators, heat from low pressure steam at conventional steam powerplants (to drive “bottoming” Rankine cycles), and geothermal heat.

The process of this invention is typically used in an organic Rankinepower cycle. Heat available at relatively low temperatures compared tosteam (inorganic) power cycles can be used to generate mechanical powerthrough Rankine cycles using working fluids as described herein. In theprocess of this invention, working fluid is compressed prior to beingheated. Compression may be provided by a pump which pumps working fluidto a heat transfer unit (e.g., a heat exchanger or an evaporator) whereheat from the heat source is used to heat the working fluid. The heatedworking fluid is then expanded, lowering its pressure. Mechanical energyis generated during the working fluid expansion using an expander.Examples of expanders include turbo or dynamic expanders, such asturbines, and positive displacement expanders, such as screw expanders,scroll expanders, and piston expanders. Examples of expanders alsoinclude rotary vane expanders.

Mechanical power can be used directly (e.g. to drive a compressor) or beconverted to electrical power through the use of electrical powergenerators. In a power cycle where the working fluid is re-used, theexpanded working fluid is cooled. Cooling may be accomplished in aworking fluid cooling unit (e.g. a heat exchanger or a condenser). Thecooled working fluid can then be used for repeated cycles (i.e.,compression, heating, expansion, etc.). The same pump used forcompression may be used for transferring the working fluid from thecooling stage.

Also provided is a method for detecting a leak from a containercomprising sampling the air in the vicinity of the container anddetecting at least one additional compound or at least one tracercompound with means for detecting the leak, wherein the composition ofthe present invention comprising HFO-1336mzz-E is contained inside thecontainer.

A container may be any known container or system or apparatus that isfilled with HFO-1336mzz-E. A container may include but is not limited toa storage container, a transport container, an aerosol can, a fireextinguishing system, a chiller apparatus, a heat pump apparatus, heattransfer container, and a power cycle apparatus (e.g., an organicRankine cycle system).

Means for detecting a leak may be any known sensor designed to detectleaks. In particular, means for detecting the leak includes, but is notlimited to, electrochemical, corona discharge and mass spectroscopicleak detectors.

By “in the vicinity of” the container is meant within 12 inches of theoutside surface of the container. Alternatively, in the vicinity may bewithin 6 inches, within 3 inches or within one inch of the outsidesurface of the container.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The following specific embodiments are, therefore, to beconstrued as merely illustrative, and do not constrain the remainder ofthe disclosure in any way whatsoever.

EXAMPLES Example 1 Polyisocyanate-Based Foam Examples

To demonstrate effectiveness of low level chlorinated compounds inHFO-1336mzz-E blowing agent, polyurethane and polyisocyanurate foamsamples are prepared by hand-mixing, using the two basic polyurethanefoam formulations described in Example 1A and Example 1B below. Theblowing agents may be generally premixed with the polyol or B-side forconvenience. Foams may be prepared either as free-rise or moldedsamples. For free-rise foams, the reaction mixture is poured into anopen, round cardboard container. For molded foams, the reaction mixtureis poured into a 2½″×13″×15″ (6.35 cm×30.02 cm×38.1 cm) heated aluminummold.

Example 1A: Polyisocyanurate Foam

All components except the isocyanate are premixed as a B-side. Theisocyanate (A-side) is then added and mixed with a mechanical stirrerfor 10 seconds. The foam reaction mixture is poured into a closedaluminum mold warmed to about 100° F. and allowed to expand. When cured,a 1″×1″×12″ sample is cut from the core of the molded foam.

Parts by Weight Blowing Agent Blowing Agent with without chlorinated 0.9wt % chlorinated Component compounds compounds aromatic polyester polyol120 120 polysiloxane surfactant 1.8 1.8 potassium octanoate catalyst 3.23.2 Tris-2,4,6- 0.4 0.4 (dimethylaminomethyl)phenol/Bis(di-methylaminomethyl)phenol catalyst E-1,1,1,4,4,4 Hexafluooro-2-butene 8080 (HFO-1336mzz-E) Blowing Agent polymethylene polyphenylisocyanate 190190 isocyanate B-side Mixture Slightly cloudy Clear Foam Density -pounds/ft³ (PCF) 2.2 2.1 Cell structure Uniform cell Exceptionally finestructure cell structure Dimensional Stability Good Good R-value/inch atmean 7.4 8.5 temperature of 75° F.

Example 1B: Polyurethane Pour-in-Place Foam

All components except the isocyanate are premixed as a B-side. Theisocyanate (A-side) is then added and mixed with a mechanical stirrerfor 10 seconds. The foam reaction mixture is poured into a closedaluminum mold warmed to about 100° F. and allowed to expand. When cured,a 1″×1″×12″ sample is cut from the core of the molded foam.

Parts by Weight Blowing Agent Blowing Agent with without chlorinated 0.9wt % chlorinated Component compounds compounds sucrose/glycerineinitiated 140 140 polyether polyol silicone surfactant 3.0 3.0N,N-Dimethylcyclohexylamine 1.7 1.7 catalystpentamethyldiethylenetriamine 0.4 0.4 catalyst 2-Methyl(n-methyl amino0.5 0.5 b-sodium acetate nonyl phenol) catalyst Water 2.1 2.1E-1,1,1,4,4,4 Hexafluooro-2-butene 70 70 (HFO-1336mzz-E) Blowing Agentpolymethylene 169 169 polyphenylisocyanate isocyanate B-side MixtureSlightly cloudy Clear Foam Density - pounds/ft³ (PCF) 2.0 1.9 Cellstructure Uniform cell Exceptionally fine structure cell structureDimensional Stability Good Good R-value/inch at mean 5.0 6.5 temperatureof 75° F.

Example 2 Effect of Low Level Chlorinated Compounds on AerosolPropellant Solubility

Unsaturated fluorocarbons exhibit different solubility than othertypically used fluorocarbon propellants. Their reduced solubility canmake it difficult to produce single phase aqueous homogenous aerosolformulations. The presence of low level chlorinated compounds canimprove mixing and ease formulations and use of aerosol products.

Example 2A: 55% VOC Hair Spray

A 55% VOC (volatile organic compound) hairspray is formulated asfollows:

Wt % Propellant without Propellant with 0.9 chlorinated wt % chlorinatedIngredient compounds compounds Octylacrylamide/acrylates/butylaminoethyl5 5 methylacrylate copolymer AMP (2-amino-2-methyl-1-propanol) 1 1 Water3 3 Ethanol 47 47 E-HFO-1336mzz Propellant 27 27 Propane 17 17 VaporPressure @ 70° F. 30 psig 20 psig Miscibility The formulation does Theformulation is one not mix easily and phase indicating shows variablespray complete miscibility patterns and delivery. and shows good spraypatterns and delivery.

Example 2B: Air Freshener

An air freshener is formulated as follows:

Wt % Propellant without Propellant with 0.9 chlorinated wt % chlorinatedIngredient compounds compounds Fragrance - mixed flower scent 1 1 Water3 3 Ethanol 24 24 E-HFO-1336mzz Propellant 49 49 Propane 23 23 VaporPressure @ 70° F. 45 psig 30 psig Miscibility The formulation does Theformulation is one not mix easily and phase indicating shows variablespray complete miscibility patterns and delivery. and shows good spraypatterns and delivery.

Example 2C: Fragrance

A fragrance is formulated as follows:

Wt % Propellant without Propellant with 0.9 chlorinated wt % chlorinatedIngredient compounds compounds Perfume 3 3 Water 10 10 Ethanol 54 54E-HFO-1336mzz 10 10 Propellant Propane 23 23 Vapor Pressure 30 psig 10psig @ 70° F. Miscibility The formulation does The formulation is onenot mix easily and phase indicating shows variable spray completemiscibility patterns and delivery. and shows good spray patterns anddelivery.

Example 3

It is critical to be able to identify leaks in refrigerant systems toavoid costly re-charging of refrigerant, ensure proper operation andprevent excessive environmental contamination.

Example 3A

Compositions of the present invention are prepared in suitablecontainer. A comparative composition that does not contain tracercompositions are also prepared. Compositions are then leaked in thevapor phase in the presence of a hand-held Ritchie Yellow Jacket®Accuprobe® heated electrochemical detector. The digital readout scale is0 for no detection to 9for maximum detection. Results are shown below.

Detector Digital Composition Reading E-HFO-1336mzz 1 E-HFO-1336mzz/0.03wt % HCC40 4 E-HFO-1336mzz/0.03 wt % HCFO-1223 4 E-HFO-1336mzz/0.03 wt %CFC-113a 4 E-HFO-1336mzz/0.03 wt % CFC-113 4 E-HFO-1336mzz/0.03 wt %HCFC-123a 4 E-HFO-1336mzz/0.03 wt % chlorobutane 4 E-HFO-1336mzz/0.03 wt% HCFC-123 4 E-HFO-1336mzz/0.03 wt % HCFC-133a 4 E-HFO-1336mzz/0.03 wt %HCFO-1122 4 E-HFO-1336mzz/0.03 wt % HCFO-1122a 4 E-HFO-1336mzz/0.03 wt %HCFO-1335 4 E-HFO-1336mzz/0.03 wt % HCFO-1326 4

The data show that addition of additional compound/tracer improves theability of the detector to detect a E-HFO-1336mzz leak.

Example 3B

Compositions of the present invention are prepared in a suitablecontainer. A comparative composition that does not include a tracer isalso prepared. Compositions are then leaked in the vapor phase in thepresence of a hand-held TIF Instruments 5650 corona discharge halogenleak detector and the detector reading are recorded based on number ofred lights illuminated. Results are shown below.

Detector Reading Composition (number of red lights) E-HFO-1336mzz 0E-HFO-1336mzz/0.03 wt % HCC-40 6 E-HFO-1336mzz/0.03 wt % HCFO-1223 6E-HFO-1336mzz/0.03 wt % CFC-113a 6 E-HFO-1336mzz/0.03 wt % CFC-113 6E-HFO-1336mzz/0.03 wt % HCFC-123a 6 E-HFO-1336mzz/0.03 wt % chlorobutane6 E-HFO-1336mzz/0.03 wt % HCFC-123 6 E-HFO-1336mzz/0.03 wt % HCFC-133a 6E-HFO-1336mzz/0.03 wt % HCFO-1122 6 E-HFO-1336mzz/0.03 wt % HCFO-1122a 6E-HFO-1336mzz/0.03 wt % HCFO-1335 6 E-HFO-1336mzz/0.03 wt % HCFO-1326 6

The data show that addition of additional compound/tracer enables thedetector to detect presence of a E-HFO-1336mzz leak, whereas it isunable to detect the leak without tracer present.

1. A composition comprising E-HFO-1336mzz and at least one additionalcompound selected from the group consisting of HFO-1243zf, HCC-40,HCFO-1223, CFC-113a, CFC-113, CFC-11, HFO-1429, HFC-449, HFO-1327,HFO-1132, HCFC-123a, chlorobutane, ethyl benzene, o-xylene, m-xylene,and p-xylene, wherein the composition contains less than about 1 weightpercent of said additional compound, based on the total weight of thecomposition.
 2. The composition of claim 1 further comprising at leastone tracer compound selected from the group consisting of HFC-356,HCFC-123, HCFC-133a, HFC-143a, HCFO-1122, HCFO-1122a, CFO-1316,HCFO-1335, HFO-1345, and HCFO-1326.
 3. A composition comprising at leastone composition selected from the group consisting of: E-HFO-1336mzz,HFO-1429, and HCFO-1335; E-HFO-1336mzz, HFO-1429, and HFO-1345;E-HFO-1336mzz, HFO-1429, and HCFC-123; E-HFO-1336mzz, HFO-1429, andCFC-11; E-HFO-1336mzz, HFO-1429, HCFO-1335, and HFO-1345; E-HFO-1336mzz,HFO-1429, HCFO-1335, and HCFC-123; E-HFO-1336mzz, HFO-1429, HCFO-1335,and CFC-11; E-HFO-1336mzz, HFO-1429, HFO-1345, and HCFC-123;E-HFO-1336mzz, HFO-1429, HFO-1345, and CFC-11; E-HFO-1336mzz, HFO-1429,HCFO-1335, HFO-1345, and HCFC-123; E-HFO-1336mzz, HCFO-1335, andHFO-1345; E-HFO-1336mzz, HCFO-1335, and HCFC-123; E-HFO-1336mzz,HCFO-1335, and CFC-11; E-HFO-1336mzz, HCFO-1335, HFO-1345, and HCFC-123;E-HFO-1336mzz, HFO-1345, and HCFC-123; E-HFO-1336mzz, HFO-1345, andCFC-11; E-HFO-1336mzz, HFC-365, and HCFO-1326; E-HFO-1336mzz, HFC-365,and CFC-11; E-HFO-1336mzz, HFO-1243zf, and HCFO-1122; E-HFO-1336mzz,HFO-1243zf, and HCC-40; E-HFO-1336mzz, HCFO-1122, and HCC-40;E-HFO-1336mzz, HFO-1243zf, HCFO-1122, and HCC-40; E-HFO-1336mzz,CFC-113a, and HFC-365; and E-HFO-1336mzz, CFC-113a, and CFC-11. 4.(canceled)
 5. The composition of claim 1 further comprising from about 1ppm to about 1000 ppm of at least one tracer compound.
 6. Thecomposition of claim 2 wherein HFO-356 is HFO-356mff.
 7. The compositionof claim 2 wherein CFO-1316 is E-HFO-1316mxx, Z-HFO-1316mxx, orcombinations thereof.
 8. The composition of claim 2 wherein HCFO-1335 isE-HCFO-1335mzz, Z-HFO-1335mzz, E-HCFO-1335mzx, Z-HFO-1335mzx, orcombinations thereof.
 9. The composition of claim 2 wherein HFO-1345 isE-HFO-1345mzz, Z-HFO-1345mzz, HFO-1345 cm, or combinations thereof. 10.The composition of claim 2 wherein HCFO-1326 is E-HFO-1326mxz,Z-HFO-1326mxz, or combinations thereof.
 11. The composition of claim 1wherein HFO-1429 is E-HFO-1429mzy, Z-HFO-1429mzy, E-HFO-1429myz,Z-HFO-1429myz, HFO-1429cz, HFO-1429cye, or combinations thereof.
 12. Thecomposition of claim 1 wherein HFC-449 is HFC-449mfe, HFC-449mmzf, orcombinations thereof.
 13. The composition of claim 1 wherein HFC-365 isHFC-365mfc. 14-15. (canceled)
 16. A method for producing coolingcomprising evaporating a composition of claim 1 in the vicinity of abody to be cooled, and thereafter condensing said composition.
 17. Amethod for producing heat comprising condensing a composition of claim 1in the vicinity of a body to be heated, and thereafter evaporating saidcompositions.
 18. A method of forming a foam comprising: (a) adding to afoamable composition a composition of claim 1; and (b) processing thefoamable composition under conditions effective to form a foam.
 19. Aprocess for producing aerosol products comprising the step of adding acomposition of claim 1 to a formulation, including active ingredients inan aerosol container, wherein said composition functions as apropellant.
 20. A process for converting heat to mechanical energycomprising heating a working fluid comprising the composition of claim 1and thereafter expanding the heated working fluid.
 21. A method fordetecting a leak from a container comprising sampling the air in thevicinity of the container and detecting at least one additional compoundor at least one tracer compound with means for detecting the leak,wherein the composition of claim 1 is contained inside the container.